Nematicidal trifluorobutenes

ABSTRACT

The invention relates to compounds of formula (I) in which X represents halogen, and n represents 0, 1 or 2, to a process for their preparations and to their use as nematacides.

The present invention relates to novel trifiluorobutenes and their useas nematicides.

U.S. Pat. No. 3,518,172 describes trifluorobutenyl compounds which havenematicidal activity. Japanese Laid-open Patent Publication (PCT) No.500037/1988(=WO 86/07590) also describes that some kinds ofpolyhaloalkene compounds have nematicidal activity. Further, WO 95/24403describes that 4,4-difluorobutenyl compounds have nematicidal activity.Japanese Laid-open Patent Application No. 176141/1997 mentions thiazolederivatives having insecticidal and araricidal activity.

There have now been found novel trifluorobutenes of the formula (I)

in which

X represents halogen and

n represents 0, 1 or 2.

The compounds of the formula (I) in which n represents 0 can be obtainedwhen trifluorobutenes of the formula (Ia)

are reacted with a halogenating agent, optionally in the presence of oneor more inert diluents (process (A)).

The compounds of the formula (I) in which

n represents 1 or 2

can be obtained when compounds of the formula (Ib)

in which

X is the same as defined above

are reacted with an oxidizing agent, optionally in the presence of oneor more inert diluents (process (B)).

The compounds of the formula (I) of the present invention have strongnematicidal activity and show good compatibility with various crops.According to the present invention the compounds of the formula (I) havesurprisingly strong nematicidal activity compared with the knowncompounds described in the aforementioned literature.

In the present specification X preferably represents fluoro, chloro orbromo. X particularly preferably represents fluoro or chloro. X veryparticularly preferably represents chloro.

In the present specification n preferably represents 0 or 2. nparticulary preferably represents 2.

Process (A) for preparing compounds of the formula (I) of the presentinvention can be represented by the following reaction scheme in whichN-chlorosuccinimide is exemplaryly used as halogenating agent:

Process (B) for preparing compounds of the formula (I) of the presentinvention can be represented by the following reaction in which5-chloro2-(3,4,4-trifluoro-3-butenylthio)thiazole is used as a startingmaterial and m-chloroperoxybenzoic acid is exemplaryly used as oxidizingagent.

2-(3,4,4-trifluoro-3-butenylthio)thiazole is a known compound describedin Japanese Laid-open Patent Publication (PCT) No. 500037/1988 (=WO86/07590). Compounds of formula (Ib), which are used as startingmaterial in process (B), correspond to the compounds of the formula (I)of the present invention in which n represents 0 and can be synthesizedaccording to the aforementioned process (A).

Halogenating agents used in Process (A) can be agents usually used forthis purpose in organic chemistry and which are known to a personskilled in the art, including for example sulfuryl chloride,N-chlorosuccinimide, N-bromosuccinimide, trichloro-isocyanuric acid,potassium fluoride, sodium chlorate, phosphorus pentachloride, titanium(IV) chloride, chlorine gas, bromine, iodine etc.

Oxidizing agents used for the oxidation of the above-mentioned compoundsof the formula (Ib) in process (B) can be agents usually used for thispurpose in organic chemistry and which are known to a person skilled inthe art including for example hydrogen peroxide water,m-chloroperoxybenzoic acid, peroxyacetic acid, peroxy-benzoic acid,magnesium monoperoxyphthalate, potassium peroxymonosulfate, etc.

The reaction of the above-mentioned process (A) is preferably conductedin the presence of an adequate diluent. Diluents which can be used inthis process can for example be water, aliphatic, alicyclic and aromatichydrocarbons (which can be optionally chlorinated) such as hexane,cyclohexane, petroleum ether, ligroine, benzene, methylene chloride,chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene etc.;ethers, such as diethyl ether, methyl ethyl ether, di-isopropyl ether,dibutyl ether, propylene oxide, dioxane, tetrahydrofuran etc.; nitrites,such as acetonitrile, propionitrile, acrylonitrile etc.; acid amides,such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone etc.;sulfones and sulfoxides, such as dimethyl sulfoxide, sulfolane etc.

The reaction temperatures of process (A) according to the invention canbe varied over a relatively wide range. In general, temperatures in arange of between 0 and 200° C., preferably between 20 and 150° C. areemployed. The process (A) according to the invention is generallycarried out under normal pressure. However, it is possible to carry outthe process (A) under elevated pressure or under reduced pressure, ingeneral between 0.1 bar and 10 bar.

To carry out the process (A) according to the invention, the startingmaterials are generally employed in approximately equimolar amounts.However, it is also possible to use one of the components in arelatively large excess. Work-up is carried out according to customarymethods (cf. the preparation examples).

For example, the compound of the formula (I) in which n represents 0 andX represents chloro can be obtained by reacting 1-1.2 moles ofN-chlorosuccinimide with 1 mole of2-(3,4,4-trifluoro-3-butenylthio)thiazole in carbon tetrachloride underreflux by heating.

The reaction of the above-mentioned process (B) is preferably conductedin the presence of an adequate diluent. Diluents which can be used inthis process can for example be water, aliphatic, alicyclic and aromatichydrocarbons (which can be optionally chlorinated), such as hexane,cyclohexane, petroleum, ether, ligroine, benzene, toluene, xylene,methylene chloride, chloroform, carbon tetrachloride, ethylene chloride,chlorobenzene etc.; ethers, such as diethyl ether, methyl ethyl ether,di-isopropyl ether, dibutyl ether, propylene oxide, dioxane,tetrahydrofuran etc.; nitriles, such as acetonitrile, propionitrile,acrylonitrile etc.; alcohols, for example methanol, ethanol,isopropanol, butanol, ethylene glycol etc.; esters, for example ethylacetate, amyl acetate etc.; acid amides, for example dimethyl-formamide,dimethylacetamide, N-methylpyrrolidone etc.; sulfones and sulfoxides,for example dimethyl sulfoxide, sulfolane etc.; carboxylic acids, forexample formic acid, acetic acid etc.

The reaction temperatures of process (B) according to the invention canbe varied over a relatively wide range: In general, temperatures in arange of between 0 and 150° C., preferably between 0 and 120° C. areemployed. The process (B) according to the invention is generallycarried out under normal pressure. However, it is also possible to carryout the process (B) under elevated pressure or under reduced pressure,in general between 0.1 bar and 10 bar.

To carry out the process (B) according to the invention, the startingmaterials are generally employed in approximately equimolar amounts.However, it is also possible to use one of the components in arelatively large excess. Work-up is carried out according to customarymethods (cf. the preparation examples).

For example, compounds of the formula (I) in which n represents 1 can beobtained by reacting, 1-2 moles of m-chloroperoxybenzoic acid with 1mole of the compound of the formula (Ib) in methylene chloride undercooling with ice.

The compounds of the formula (I) according to the present invention showstrong controlling activity against nematodes. They can, therefore, beefficiently used as nematicidal agents. The compounds of the formula (I)of the present invention do not exhibit phytotoxicity against crops andcan be used for controlling harmful nematodes.

The compounds according to the invention can be used, for example,against nematodes such as Pratylenchus spp., Globodera spp., such asGlobodera rostochiensis wollenweber, Heterodera spp., such as Hetemoderaglycines ichinohe, Meloidogyne spp., Aphelenchoides spp., such asAphelenchoides basseyi christie, Radopholus similis, Ditylenchusdipsaci, Tyleachulus semipenetrans, Longidorus spp., Xiphinema spp.,Trichodorus spp., Bursaphelenchus spp., such as Bursaphelenchusxylophilis etc.

The compounds according to the invention are especially useful forcombating Pratylenhs spp., Globodera rostochiensis wollenweber,Heterodea glycines ichinohe, Meloidogyne spp., Aphelenchoides basseyiChristie, Bursaphelenchus xylophilis.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other nematodes.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, water dispersiblegranules, suspensions, powders, dusting agents, foaming agents, pastes,soluble powders, granules, suspo-emulsion concentrates, microcapsules,fumigants, natural and synthetic materials impregnated with activecompound and very fine capsules and polymeric substances.

These formulations are prepared in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents, liquefiedgas and/or solid diluents or carriers, if appropriate with the use ofsurface-active agents, that is emulsifiers and/or dispersants and/orfoam-formers.

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Suitable liquid solvents areessentially: aromatics, such as xylene, toluene, or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons, such aschlorobenzene, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, mineral or vegetable oil, alcohols, such as butanol orglycol, and also their ethers and esters, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclobexanone, stronglypolar solvents, such as dimethylformamide and dimethyl sulphoxide, andalso water.

Liquefied gas diluents or carriers are liquefied substances which aregases at normal temperature and pressure. Liquefied gas diluents can be,for example, aerosol propellants such as butane, propane, nitrogen gas,carbon dioxide, halogenated hydrocarbons, etc.

Suitable solid comers are:

for example ammonium salts and ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth and ground synthetic minerals, such as finely divided silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, as well as synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut she, maize cobs and tobacco stalks; suitableemulsifiers and/or foam-formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates and proteinhydrolysates; suitable dispersants are: for example lignin-sulphitewaste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.01 and 95 per cent byweight of active compound, preferably between 0.1 and 90%, particularlypreferably between 0.5 and 90%.

The active compounds according to the invention, as such or in theirformulations, can also be used in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, to widen, forexample, the activity spectrum or to prevent the development ofresistance. In many cases, this results in synergistic effects, i.e. theactivity of the mixture exceeds the activity of the individualcomponents.

Examples of particularly advantageous mixing components are thefollowing:

Fungicides:

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzarnacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupite, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylmine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,firconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulphocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quitozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenoltriazbutil, triazoxide, trichlamide, tricyclazole, tridamorph,triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zailamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethy-∃-(2-phenoxyethyl)1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-∃-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-∃-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-∃-[[4(trifluoromethyl)phenyl]-methylene]-1,2,4-triazole-1 1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4triazol-1-yl)-3-octanone,

(E)-a-methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

isoproyl1-{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanoneO-(phenylmethyl) oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrol-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2′,6′-dibromo-2-methyl-4′-trifluorometoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate,

2,6-dichloro-N-(4-tifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazol,

2-[[6-deoxy-4-O-(4-O-methyl-∃-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N(2,3-dihydro-1,1,3-trimethyl-1H-indene-4-yl)-3-pyrdinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)phenyl]1H-pyrrol-2,5-dione,

3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimthylethyl)N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)3-methyl-4[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2(1H-1,2,4-triazol-1-yl)-cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine hydrochloride,

ethyl[(4-chlorophenyl)-azo]-cyanoacetate,

potassium hydrogen carbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetahydro-2-pyrimidineamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

N-(6methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)amino]-ethyl]-benzamiide,

N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,

N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl[2-dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoraridothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate, and

spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran]-3′-one,

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/acaricide/nematicides:

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, baculoviruses, Beauveria bassiania, Beauveria tenella,bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,bifenazate, bifentrin, bioethanomethrin, bio-permethrin, BPMC, bromophosA, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb,clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin,cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos,diofenolan, disulfoton, docusat-sodium, dofenapyn,

eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,esfenvalerate, ethiofencarb, ethion, etboprophos, etofenprox, etoxazole,etrimfos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb,fenoxacrim, fenoxycarb, fenpropatin, fenpyrad, fenpyrithrin,fenpyroximate, fenvalerate, fipronil, fluazinam, flauzuron,flubrocythrinate, flucycloxuron, flucyrnate, flufenoxuron, flutenzine,fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox,furathiocarb,

granulosis viruses,

halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,

imidacloprid, isazofos, isofenphos, isoxathion, ivemectin,

nuclear polyhedrosis viruses,

lambda-cyhalothrin lufenuron

malathion, mecaibam, metaldehyde, methamidophos, Metharhiziumanisopliae, Metharhizium flavoviride, methidathion, methiocarb,methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoat, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parthion A, parathion M, permefirin,phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb,pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos,prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben,pyridathion, pyrimidifen, pyriproxyfen,

quinalphos,

ribavirin,

salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,trimethacarb, vamidothion, vaniliprole, Verticillium lecanii,

YI 5302,

zeta-cypermethrin, zolaprofos,

(1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl3-[(dihydro-2-oxo-3(2H)-furanlidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)-methyl2,2,3,3-tetraminethylcyclopropanecarboxylate,

1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,

2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]4,5-dihydro-oxazole,

2-(acetlyoxy)-3-dodecyl-1,4-naphthalenodione,

2-chloro-N-[[[4-(1-phenylethoxy)phenyl]amino]-carbonyl]-benzamide,

2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,

3-methylphenyl propylcarbamate.

4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,

4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyndazrione,

4chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyrdazinone,

4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3-(2H)-pyridazinone,

Bacillus thuringiensis strain EG-2348,

[2-benzoyl-1-(1,1-dimethylethyl)-hydrzinobenzoic acid,

2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-ylbutanoate,

[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,

dihydro-2-(nitromethylene)-2H-1,3-thiazinie-3(4H)-carboxaldehyde,

ethyl[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,

N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,

N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-diydro-4-phenyl-1H-pyrazole-1-carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,

N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,

N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,

O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoroamidothioate.

A mixture with other known active compounds, such as herbicides, or withfertilizes and growth regulators is also possible.

Furthermore, when used as nematicides, the active compounds according tothe invention can be present in their commercial formulations and in theuse forms, prepared from these formulations, as a mixture withsynergists. Synergists are compounds which increase the action of theactive compounds, without it being necessary for the synergist added tobe active itself.

The active-compound content of the use forms prepared from thecommercial formulations can vary within wide limits. The active-compoundconcentration of the use forms can be from 0.0000001 to 95% by weight ofactive compound, preferably between 0.0001 and 1% by weight. Applicationis carried out in a customary manner adapted to the use forms.

The preparation and the use of the compounds according to the presentinvention will be described more specifically by the following examples.However, the present invention should not be restricted to them in anyway. “Parts” mean “parts by weight” unless specified otherwise.

PREPARATION EXAMPLES Example 1

2-(3,4,4-Trifluoro-3-butenylthio)thiazole (6.75 g, 30 mM) is dissolvedin carbon tetrachloride (60 ml). N-chlorosuccinimide (4.8 g) is added tothe solution and refluxed for 18 hours by heating. As soon as thereaction has reached room temperature, the mixture is filtered and thesolvent is distilled off. The concentrate is purified by columnchromatography (eluent: hexane/ethyl acetate=90/10) to obtain5-chloro-2-(3,4,4-trifluoro-3-butenylthio)thiazole as pale yellow liquid(n²⁰ _(D) 1.5326).

Example 2

5-Chloro-2-(3,4,4-trifluoro-3-butenylthio)thiazole (2.07 g, 8 mM) isdissolved in chloroform (40 ml). m-chloroperoxybenzoic acid (1.38 g) isadded to the solution under ice cooling (temperature below 4° C.) andfurther stirred for 8 hours at a temperature below 4° C.

10% sodium thiosulfate is added to the solution and the solution is thenfractionated. The chloroform layer is washed with 5% aqueous solution ofsodium hydroxide and dried over unhydrous magnesium sulfate. The solventis distilled off and the concentrate is purified by columnchromatography (eluent: hexane/ethyl acetate=90/10) to obtain5-chloro-2-(3,4,4-trifluoro-3-butenylsulfinyl)thiazole (1.5 g) as paleyellow liquid (n²⁰ _(D) 1.5380).

Example 3

To the solution of 5-chloro-2-(3,4,4-trifuoro-3-butenylthio)thiazole(2.60 g, 10 mM) and acetic acid (28 g) 31% hydrogen peroxide water (3.29g) is added and stirred at 55-60° C. for 6 hours. After cooling to 5° C.the reaction mixture is adjusted to pH 6 by adding an appropriate amountof an aqueous solution of sodium hydroxide, diluted with water andextracted three times with chloroform (25 ml). The chloroform layer iswashed with water, 10% sodium thiosulfate and water in this order, anddried over unhydrous sodium sulfate. The solvent is distilled off andthe concentrate is purified by column chromatography (eluent:hexane/ethyl acetate=90/10) to obtain5-chloro-2-(3,4,4-trifluoro-3-butenylsulfonyl)thiazole (2.2 g) as paleyellow liquid (n²⁰ _(D) 1.5205).

REFERENCE EXAMPLE

2-Mercaptothiazole (5.18 g), potassium carbonate (6.72 g) and4-bromo-1,1,2-trifluorobutene-1 (9.21 g) are refluxed in acetonitrile(60 ml) in the presence of argon gas for 6 hours by heating. After thereaction mixture has reached room temperature, it is filtered and thesolvent is distilled off. The residue is dissolved in dichloromethaneand washed with 5% aqueous solution of sodium hydroxide and water inthis order. It is dried over unhydrous sodium sulfate and purified bycolumn chromatography (eluent: dichloromethane) to obtain2-(3,4,4-trifluoro-3-butenyl-thio)thiazole (8.6 g) as pale yellow liquid(n²⁰ _(D) 1.5200).

USE EXAMPLES Example 1 Test Against Meloidogyne spp. Soil pot Test

Preparation of Test Agent:

1 Part of the active compound is impregnated to 99 parts of pumice toobtain fine granules.

Test Method:

The test agent prepared as mentioned above was added to soilcontaminated with Meloidogyne incognita to a chemical concentration of10 ppm and homogeneously mixed by stirring. A pot (1/5000 are) wasfilled with the soil. About 20 seeds of tomato (variety: Kurihara) weresown per pot. After cultivation in a greenhouse for 4 weeks, they werecarefully pulled out not to damage the roots and the root knot index andthe controlling effect were determined as follows.

Degree of damage 0: No knots were formed (Complete control).

1: A few knots were formed.

2: Knots were formed to a medium extent.

3: Knots were formed to an intense extent.

4: Knots were formed to the most intense extent (which corresponds tonon-treatment).${{Root}\quad {knot}\quad {index}} = {\frac{\sum\limits^{\quad}\quad \left( {{degree}\quad {of}\quad {damage} \times {number}\quad {of}\quad {individuals}} \right)}{{Total}\quad {number}\quad {of}\quad {tested}\quad {individuals} \times 4} \times 100}$

The controlling effect of the compounds tested can then be evaluatedaccording to the following equation:${{Controlling}\quad {{effect}\lbrack\%\rbrack}} = {\frac{\left( {\begin{matrix}{{Root}\quad {knot}\quad {index}\quad {at}} \\{{non}\text{-}{treated}\quad {area}}\end{matrix} - \begin{matrix}{{Root}\quad {knot}\quad {index}\quad {at}} \\{{treated}\quad {area}}\end{matrix}} \right)}{{Root}\quad {knot}\quad {index}\quad {at}\quad {non}\text{-}{treated}\quad {area}} \times 100}$

The evaluation of the controlling effects of the compounds according tothe present invention was done on the basis of the values of thecontrolling effect which can be obtained in the above-mentioned way andwere connected with the following standards:

a: Controlling effect 100-71%

b: Controlling effect 70-50%

c: Controlling effect less than 50%

d: Controlling effect 0%

Results are shown in the following Table 1.

TABLE 1 Compound Concentration of active ingredient Evaluation of Ex.No. [ppm] controlling effect 1 10 a 2 10 a 3 10 a

FORMULATION EXAMPLES Example 1 Granule

To a mixture of 10 parts of a compound according to the presentinvention (Example No. 1), 30 parts of bentonite (montmorillonite), 58parts of talc and 2 parts of ligninsulphonate salt, 25 parts water areadded, well kneaded, worked up into granules of 10-40 mesh with the helpof an extrusion granulator and dried at 40-50° C. to obtain granules.

Example 2 Granule

95 Parts of clay mineral particles having a particle diameterdistribution of 0.2-2 mm are put into a rotary mixer. While rotating it,5 parts of a compound according to the present invention (Example No. 2)are sprayed onto the mineral particles together with a liquid diluent toobtain uniformly wetted particles and the particles are then dried at40-50° C. to obtain granules.

Example 3 Emulsifiable Concentrates

30 Parts of a compound according to the present invention (Example No.3), 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl etherand 7 parts of calcium alkylbenzenesulphonate are mixed and stirred toobtain an emulsion.

Example 4 Wettable Powder

15 parts of a compound according to the present invention (Example No.1), 80 parts of a mixture of white carbon (hydrous amorphous siliconoxide fine powders) and powder clay (1:5), 2 parts of sodiumalkylbenzenesulphonate and 3 parts of sodiumalkylnaphthalenesulphonate-formalin-condensate are crushed and mixedtogether to obtain a wettable powder.

What is claimed is:
 1. A compound of the Formula (I)

wherein X represents halogen, and n represents 0, 1 or
 2. 2. A compound of the Formula (I) according to claim 1, wherein X represents fluoro, chloro or bromo, and n represents 0 or
 2. 3. A compound of the Formula (I) according to claim 1 wherein X represents chloro or bromo, and n represents
 2. 4. A compound of the Formula (I) according to claim 1 wherein X represents chloro.
 5. A process for preparing a compound of the Formula (I)

wherein X is as defined in one of claims 1 to 4, and n represents 0, comprising the step of: reacting 2-(3,4,4-trifluoro-3-butenylthio)thiazole with a halogenating agent, optionally in the presence of an inert solvent.
 6. A process for preparing a compound of the Formula (I)

wherein n represents 1 or 2, and X is as defined in one of claims 1 to 4, comprising the step of: reacting a compound of the Formula (Ib)

wherein X is as defined in one of claims 1 to 4, with an oxidizing agent, optionally in the presence of an inert solvent.
 7. A nematicidal composition comprising at least one compound of the Formula (I) according to one of claims 1 to
 4. 8. A method of combating nematodes, comprising the step of allowing an effective amount of a compound of the Formula (I) according to one of claims 1 to 4 to act on a member selected from the group consisting of nematodes, a habitat of said nematodes and combinations thereof.
 9. A process for preparing a nematicidal composition, comprising the step of mixing a compound of the Formula (I) according to one of claims 1 to 4 with a member selected from the group consisting of an extender a surface active agent and combinations thereof. 